CN110283111A - A method of preparing the anhydrous Perbutyric Acid for synthesizing 6-caprolactone - Google Patents
A method of preparing the anhydrous Perbutyric Acid for synthesizing 6-caprolactone Download PDFInfo
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- CN110283111A CN110283111A CN201910601029.8A CN201910601029A CN110283111A CN 110283111 A CN110283111 A CN 110283111A CN 201910601029 A CN201910601029 A CN 201910601029A CN 110283111 A CN110283111 A CN 110283111A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
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- C07D313/04—Seven-membered rings not condensed with other rings
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Abstract
The invention discloses a kind of preparation methods of anhydrous Perbutyric Acid: adding a dehydrating tower using a reaction kettle, in reaction kettle upper end, reaction tower tower reactor connects an adsorption tower.Catalyst, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, after being stirred, hydrogen peroxide is added dropwise using titration tank and reaction kettle is added, reaction kettle uses jacket reactor, and cooling water coil is contained in collet, and reaction kettle band stirs to make to react uniform progress, in distillation rectifying tower top recovered water and organic solvent, tower reactor generates Perbutyric Acid solution, squeezes into adsorption tower by product pump, and further dehydration prepares anhydrous Perbutyric Acid.
Description
Technical field
The invention belongs to chemical technology fields, are related to a kind of method for preparing anhydrous Perbutyric Acid, are especially used to prepare
The method of the anhydrous Perbutyric Acid of 6-caprolactone.
Background technique
Peroxycarboxylic acid is a kind of important organic peroxide, has many advantages, such as that oxidisability is strong, good with organic matter compatibility,
The oxidant being commonly used in organic synthesis, prepares fine chemical product.With Peracetic acid using more in peroxycarboxylic acid, still
Peracetic acid is extremely unstable, easily decomposes and explodes.Perbutyric Acid compares Peracetic acid, and thermal stability increases, more suitable for industry
Production.
6-caprolactone (ε-CL) is a kind of important organic synthesis intermediate, be mainly used for synthesizing polycaprolactone polyol,
The copolymerization and modification of polycaprolactone and other esters polymers, because polycaprolactone has good nontoxicity, biological degradability, compatible
Property, seep pharmacological property, so its degradative plastics and biomedicine in obtain preferable application.
It is raw that generally by cyclohexanone, peroxycarboxylic acid Baeyer-Wei Li reaction grid occurs under certain condition for the synthesis of 6-caprolactone
At.
The production technology of 6-caprolactone monomer is grasped by 3 enterprises, foreign countries at present, and the country only has a set of 6-caprolactone list
The industrial production equipment of body.
The synthesis technology of 6-caprolactone is divided into cyclohexanone and non-cyclohexanone route.Cyclohexanone route is divided into peroxide acid oxidase again
Method, hydrogen peroxide oxidation method and oxygen/air oxidizing process etc..
American Association carbon compound company in 1967 synthesizes 6-caprolactone using Peracetic acid peroxyester.With cyclohexanone
For raw material, the acetone or ethyl acetate solution of anhydrous peroxyacetic acid are oxidant.
2005, Japanese Daicel realized the industrialization of 6-caprolactone using Peracetic acid oxidation route.
2011, Hunan University proposed hydrogen peroxide-acetic anhydride route, under the action of catalyst, hydrogen peroxide and acetic anhydride
Reaction preparation Peracetic acid.
Middle petrochemical industry Ba Ling petrochemical industry was in proposition dioxygen water-propionic acid route in 2012, and using propionic acid as solvent, hydrogen peroxide preparation is added
Perpropionic Acid, Perpropionic Acid peroxyester prepare 6-caprolactone.
2013, Feixiang Chemical Co., Ltd., Jiangsu cooperated with Zhongshan University, was to urge with magnesium or tin metalloporphyrin complex
Agent is reacted by air or oxygen with benzaldehyde in esters solvent, and the high conversion rate of cyclohexanone is in 95%, but by-product
Benzoic acid separated with caprolactone difficulty.
In the reaction process of cyclohexanone and percarboxylic acids, 6-caprolactone can because hydrolysis, autohemagglutination and generate hydroxycaproic acid, oneself two
The substances such as acid and polycaprolactone oligomer reduce the yield of caprolactone to increase the separating difficulty of caprolactone.
During preparing Perbutyric Acid, since hydrogen peroxide contains a large amount of water, while water is also generated during the preparation process, because
And contain a large amount of water in aqueous peroxycarboxylic acid solution, in order to reduce the influence to oxidizing cyclohexanone reaction, it is organic to be typically chosen addition
Solvent sloughs the moisture in aqueous peroxycarboxylic acid solution by azeotropic distillation mode.It is removed in aqueous peroxycarboxylic acid solution by azeotropic distillation
Moisture, the rectifying time needed is very long, generally once intermittently needs the rectifying time 12 hours, can reduce the production energy of device in this way
Power.
CN108863883A describes a kind of method prepared without the anhydrous Perpropionic Acid of catalyst, is reacted using 4-5
Rectifying column series connection and a distillation rectifying column, charging hydrogen peroxide, catalyst, light component, phosphate are passed sequentially through by premixing
It is pumped into the tower body of continuous 4-5 reactive distillation column, reactive distillation is carried out in reactive distillation column, the last one reactive distillation
Tower tower bottoms is free of the anhydrous Perpropionic Acid of catalyst into distillation rectifying column, in the extraction of distillation the top of the distillation column, and tower reactor, which contains, urges
Agent and phosphate are recycled back to first reactive distillation column.
CN105646433A describes a kind of technique for continuously preparing high-purity caprolactone, which is characterized in that using reaction and separation
Integrated apparatus device is carried out continuously the preparation of Peracetic acid and/or Perpropionic Acid and separates the preparation with caprolactone and separate；
The reaction and separation integrated apparatus by be sequentially connected catalytic rectifying column, reactive distillation column, stirred autoclave and
Rectifying column composition, the rectifying column includes rectifying 1# tower and rectifying 2# tower；When carrying out continuous production, acetic acid and/or third will be contained
The organic solution of acid and the aqueous solution containing hydrogen peroxide are continually introduced into catalytic rectifying column from catalytic rectifying column top
It is mixed, while catalytic oxidation occurs under storng-acid cation exchange resin effect, carrying out catalytic oxidation
While, water and organic solvent in reaction mixture pass through distillation side from the tower top of catalytic rectifying column as an azeotrope
Formula is drawn；The Peracetic acid and/or Perpropionic Acid and ORGANIC SOLVENT MIXTURES that catalytic oxidation generates are smart from catalyst reaction
The tower bottom for evaporating tower introduces reactive distillation tower bottom, is contacted with the cyclohexanone for entering reactive distillation column in the middle part of reactive distillation column
And oxidation reaction occurs, obtained oxidation reaction product introduces stirred autoclave and further reacts, that is, arrives caprolactone crude liquid；Gained
Caprolactone crude liquid is introduced into rectifying 1# column distillation and isolates low boiling point organic solvent and organic carboxyl acid, enters back into rectifying 2# column distillation
High-boiling-point impurity is isolated, the caprolactone that purity is not less than 99.5% is continuously available；It is wherein organic molten containing acetic acid and/or propionic acid
The organic solvent used in liquid is one or more in ethyl acetate, propyl acetate, isopropyl acetate and ethyl propionate.Above-mentioned two
Patent has used the series connection of multiple rectifying columns during preparing Perpropionic Acid, this will increase rectifying column, thus the throwing in equipment
Money can greatly increase；Perpropionic Acid is easy to decompose simultaneously, and addition stabilizer could reduce the decomposition of Perpropionic Acid, so that preparing oneself
Reaction efficiency during lactone improves.An adsorption tower is connected in reactor bottom, is packed into molecular sieve in adsorption tower, further
The moisture for reducing Perbutyric Acid solution, to reduce the generation of side reaction in 6-caprolactone rectifying purification process.
Summary of the invention
Object of the present invention is to invent a kind of to prepare the 6-caprolactone method of anhydrous Perbutyric Acid.
Realize the technical solution of the object of the invention:
A kind of preparation method of anhydrous Perbutyric Acid, it is characterised in that add one to take off using a reaction kettle, in reaction kettle upper end
Water tower, reaction tower tower reactor connect an adsorption tower.Reaction kettle is added by titration tank in catalyst, stabilizer, organic solvent, butyric acid
In, after being stirred, hydrogen peroxide is added dropwise using titration tank and reaction kettle is added, and reaction kettle uses jacket reactor, contains in collet
Cooling water coil, reaction kettle band stirs to make to react uniform progress, in distillation rectifying tower top recovered water and organic solvent, tower reactor
Perbutyric Acid solution is generated, adsorption tower is squeezed by product pump, further dehydration prepares anhydrous Perbutyric Acid.
The method for preparing anhydrous Perbutyric Acid, it is characterised in that the catalyst refers to boric acid, metaboric acid, immobilized sulphur
The one of which such as sour, immobilized phosphoric acid, acid cation exchange resin.
The method for preparing anhydrous Perbutyric Acid, it is characterised in that reaction carries out under negative pressure state, absolute pressure 1-
20KPa。
The method for preparing anhydrous Perbutyric Acid, it is characterised in that the mass ratio of catalyst and hydrogen peroxide is
0.01-0.2。
The reaction temperature of Perbutyric Acid is 40-70 DEG C.
The stabilizer is pyridine carboxylic acid, pyridinedicarboxylic acid one of which.
The method for preparing anhydrous Perbutyric Acid, it is characterised in that organic solvent used is ethyl acetate, acetic acid
One of propyl ester, isopropyl acetate, butyl acetate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate.
The method for preparing anhydrous Perbutyric Acid, it is characterised in that wherein the mass ratio of organic solvent and butyric acid is
0.2-1。
Filler used in adsorption tower is 3A molecular sieve.
The features of the present invention and effect
The present invention use reaction kettle, dehydrating tower and adsorption tower combination, realize and prepare Perbutyric Acid serialization, reaction it is same
When, by the moisture in dehydrating tower removing system, reaction heat can be made full use of, reduces energy needed for azeotropic distillation is dehydrated.
Due to being added to stabilizer, Perbutyric Acid degradation is substantially reduced, and reaction efficiency improves.Adsorption tower can sufficiently reduce peroxide simultaneously
The moisture of butyric acid solution generates to reduce production caprolactone byproduct in process object.
Specific embodiment
The present invention is further described below with reference to embodiment, but is not intended to limit protection scope of the present invention.
Embodiment 1
The preparation method of anhydrous Perbutyric Acid solution: a reaction kettle with stirring adds a dehydrating tower in reaction kettle upper end.It urges
Agent, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, and after mixing evenly, hydrogen peroxide passes through titration tank drop
Enter reaction kettle.Reaction is performed under reduced pressure, and the water in system is removed while reacting, and is lower than to kettle base solution moisture
When 0.15%, kettle base solution is squeezed at the top of adsorption tower by product pump, by obtaining anhydrous Perbutyric Acid after adsorption tower.Anhydrous peroxide
Butyric acid and hexamethylene reactive ketone generate caprolactone.
Dehydrating tower operating pressure is controlled in 15-20KPa (absolute pressure).
It is sieve-plate tower that dehydrating tower, which uses,.
The reaction temperature of Perbutyric Acid is 50 DEG C.
The mass ratio of catalyst and hydrogen peroxide is 0.02.
Stabilizer is pyridine carboxylic acid.
Organic solvent is ethyl propionate.
The mass ratio of organic solvent and butyric acid is 0.3.
From the water discharge system in the azeotropic mixture that tower top distillates, ethyl propionate is back in tower.
By obtaining Perbutyric Acid solution after adsorption tower: Perbutyric Acid 20.2%, hydrogen peroxide is less than 0.1%, water content
For 0.01% (mass content).
The conversion ratio of hydrogen peroxide is 99.1%, and the selectivity of Perbutyric Acid is 96.4%.
The Perbutyric Acid of preparation synthesizes caprolactone, and yield reaches 94%, by-product 6%.
Embodiment 2
The preparation method of anhydrous Perbutyric Acid solution: a reaction kettle with stirring adds a dehydrating tower in reaction kettle upper end.It urges
Agent, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, and after mixing evenly, hydrogen peroxide passes through titration tank drop
Enter reaction kettle.Reaction is performed under reduced pressure, and the water in system is removed while reacting, and is lower than to kettle base solution moisture
When 0.15%, kettle base solution is squeezed at the top of adsorption tower by product pump, by obtaining anhydrous Perbutyric Acid after adsorption tower.Anhydrous peroxide
Butyric acid and hexamethylene reactive ketone generate caprolactone.
Dehydrating tower operating pressure is controlled in 10-15KPa (absolute pressure).
It is sieve-plate tower that dehydrating tower, which uses,.
The reaction temperature of Perbutyric Acid is 50 DEG C.
The mass ratio of catalyst and hydrogen peroxide is 0.05.
Stabilizer is pyridinedicarboxylic acid
Organic solvent is ethyl propionate.
The mass ratio of organic solvent and butyric acid is 0.4.
From the water discharge system in the azeotropic mixture that tower top distillates, organic solvent is back in tower.
Adsorption tower tower bottom obtains: Perbutyric Acid 21.1%, and for hydrogen peroxide less than 0.1%, water content is 0.007% (quality
Content).
The conversion ratio of hydrogen peroxide is 99.2%, and the selectivity of Perbutyric Acid is 95.8%.
The Perbutyric Acid of preparation synthesizes caprolactone, and yield reaches 94.2%, by-product 5.8%.
Embodiment 3
The preparation method of anhydrous Perbutyric Acid solution: a reaction kettle with stirring adds a dehydrating tower in reaction kettle upper end.It urges
Agent, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, and after mixing evenly, hydrogen peroxide passes through titration tank drop
Enter reaction kettle.Reaction is performed under reduced pressure, and the water in system is removed while reacting, and is lower than to kettle base solution moisture
When 0.15%, kettle base solution is squeezed at the top of adsorption tower by product pump, by obtaining anhydrous Perbutyric Acid after adsorption tower.Anhydrous peroxide
Butyric acid can generate caprolactone with hexamethylene reactive ketone.
Dehydrating tower operating pressure is controlled in 7-10KPa (absolute pressure).
It is sieve-plate tower that dehydrating tower, which uses,.
The reaction temperature of Perbutyric Acid is 60 DEG C.
The mass ratio of catalyst and hydrogen peroxide is 0.09.
Stabilizer is pyridinedicarboxylic acid.
Organic solvent is propyl propionate.
The mass ratio of organic solvent and butyric acid is 0.5.
From the water discharge system in the azeotropic mixture that tower top distillates, organic solvent is back in tower.
Adsorption tower tower bottom obtains: Perbutyric Acid 21.2%, and for hydrogen peroxide less than 0.1%, water content is 0.008% (quality
Content).
The conversion ratio of hydrogen peroxide is 99.1%, and the selectivity of Perbutyric Acid is 95.5%.
The Perbutyric Acid of preparation synthesizes caprolactone, and yield reaches 93.8%, by-product 6.2%.
Embodiment 4
The preparation method of anhydrous Perbutyric Acid solution: a reaction kettle with stirring adds a dehydrating tower in reaction kettle upper end.It urges
Agent, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, and after mixing evenly, hydrogen peroxide passes through titration tank drop
Enter reaction kettle.Reaction is performed under reduced pressure, and the water in system is removed while reacting, and is lower than to kettle base solution moisture
When 0.15%, kettle base solution is squeezed at the top of adsorption tower by product pump, by obtaining anhydrous Perbutyric Acid after adsorption tower.Anhydrous peroxide
Butyric acid and hexamethylene reactive ketone generate caprolactone.
Dehydrating tower operating pressure is controlled in 5-7KPa (absolute pressure).
It is sieve-plate tower that dehydrating tower, which uses,.
The reaction temperature of Perbutyric Acid is 60 DEG C.
The mass ratio of catalyst and hydrogen peroxide is 0.1.
Stabilizer is pyridine carboxylic acid.
Organic solvent is butyl propionate.
The mass ratio of organic solvent and butyric acid is 0.4.
From the water discharge system in the azeotropic mixture that tower top distillates, butyl propionate is back in tower.
Reaction tower tower reactor obtains: Perbutyric Acid 20.9%, and for hydrogen peroxide less than 0.1%, water content is that 0.01% (quality contains
Amount).
The conversion ratio of hydrogen peroxide is 99.0%, and the selectivity of Perbutyric Acid is 95.6%.
The Perbutyric Acid of preparation synthesizes caprolactone, and yield reaches 93.6%, by-product 6.4%.
Embodiment 5
The preparation method of anhydrous Perbutyric Acid solution: a reaction kettle with stirring adds a dehydrating tower in reaction kettle upper end.It urges
Agent, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, and after mixing evenly, hydrogen peroxide passes through titration tank drop
Enter reaction kettle.Reaction is performed under reduced pressure, and the water in system is removed while reacting, and is lower than to kettle base solution moisture
When 0.15%, kettle base solution is squeezed at the top of adsorption tower by product pump, by obtaining anhydrous Perbutyric Acid after adsorption tower.Anhydrous peroxide
Butyric acid and hexamethylene reactive ketone generate caprolactone.
Dehydrating tower operating pressure is controlled in 1-5KPa (absolute pressure).
It is sieve-plate tower that dehydrating tower, which uses,.
The reaction temperature of Perbutyric Acid is 60 DEG C.
The mass ratio of catalyst and hydrogen peroxide is 0.15.
Stabilizer is pyridine carboxylic acid.
Organic solvent is ethyl propionate.
The mass ratio of organic solvent and butyric acid is 0.5.
From the water discharge system in the azeotropic mixture that tower top distillates, organic solvent is back in tower.
Adsorption tower tower bottom obtains: Perbutyric Acid 21.4%, and hydrogen peroxide is less than 0.1%, water content 0.006%.
The conversion ratio of hydrogen peroxide is 99.2%, and the selectivity of Perbutyric Acid is 95.7%.
The Perbutyric Acid of preparation synthesizes caprolactone, and yield reaches 94.5%, by-product 5.5%.
Embodiment 6
The preparation method of anhydrous Perbutyric Acid solution: a reaction kettle with stirring adds a dehydrating tower in reaction kettle upper end.It urges
Agent, stabilizer, organic solvent, butyric acid are added in reaction kettle by titration tank, and after mixing evenly, hydrogen peroxide passes through titration tank drop
Enter reaction kettle.Reaction is performed under reduced pressure, and the water in system is removed while reacting, and is lower than to kettle base solution moisture
When 0.15%, kettle base solution is squeezed at the top of adsorption tower by product pump, by obtaining anhydrous Perbutyric Acid after adsorption tower.Anhydrous peroxide
Butyric acid can generate caprolactone with hexamethylene reactive ketone.
Dehydrating tower operating pressure is controlled in 7-15KPa (absolute pressure).
It is sieve-plate tower that dehydrating tower, which uses,.
The reaction temperature of Perbutyric Acid is 70 DEG C.
The mass ratio of catalyst and hydrogen peroxide is 0.18.
Stabilizer is pyridinedicarboxylic acid.
Organic solvent is ethyl propionate.
The mass ratio of organic solvent and butyric acid is 0.6.
From the water discharge system in the azeotropic mixture that tower top distillates, ethyl propionate is back in tower.
Adsorption tower tower bottom obtains: Perbutyric Acid 20.3%, and for hydrogen peroxide less than 0.1%, water content is 0.009% (quality
Content).
The conversion ratio of hydrogen peroxide is 99.2%, and the selectivity of Perbutyric Acid is 95.1%.
The Perbutyric Acid of preparation synthesizes caprolactone, and yield reaches 93.4%, by-product 6.6%.
Claims (8)
1. a kind of preparation method of anhydrous Perbutyric Acid, it is characterised in that add one using a reaction kettle, in reaction kettle upper end
Dehydrating tower, reaction tower tower reactor connect an adsorption tower.Reaction is added by titration tank in catalyst, stabilizer, organic solvent, butyric acid
In kettle, after being stirred, hydrogen peroxide is added dropwise using titration tank and reaction kettle is added, and reaction kettle uses jacket reactor, in collet
Containing cooling water coil, reaction kettle band is stirred to make to react uniform progress, in distillation rectifying tower top recovered water and organic solvent, tower
Kettle generates Perbutyric Acid solution, squeezes into adsorption tower by product pump, and further dehydration prepares anhydrous Perbutyric Acid.
2. preparing the method for anhydrous Perbutyric Acid described in claim 1, it is characterised in that the catalyst refer to boric acid, partially
The one of which such as boric acid, immobilized sulfuric acid, immobilized phosphoric acid, acid cation exchange resin.
3. preparing the method for anhydrous Perbutyric Acid described in claim 1, it is characterised in that reaction carries out under negative pressure state,
Absolute pressure is 1-20KPa.
4. preparing the method for anhydrous Perbutyric Acid described in claim 1, it is characterised in that the matter of catalyst and hydrogen peroxide
Amount is than being 0.01-0.2.
5. the reaction temperature of Perbutyric Acid described in claim 1 is 40-70 DEG C.
6. stabilizer described in claim 1 is pyridine carboxylic acid, pyridinedicarboxylic acid one of which.
7. preparing the method for anhydrous Perbutyric Acid described in claim 1, it is characterised in that organic solvent used is acetic acid
Ethyl ester, propyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, propyl propionate, isopropyl propionate, one in butyl propionate
Kind.
8. preparing the method for anhydrous Perbutyric Acid described in claim 1, it is characterised in that wherein organic solvent and butyric acid
Mass ratio is 0.2-1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032565A (en) * | 2021-11-12 | 2022-02-11 | 万华化学集团股份有限公司 | Preparation method and application of anhydrous peroxycarboxylic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070639A (en) * | 1991-09-20 | 1993-04-07 | 宇部兴产株式会社 | The preparation method of perpropionic acid |
| CN106349140A (en) * | 2016-10-26 | 2017-01-25 | 湖南聚仁化工新材料科技有限公司 | Method for preparing anhydrous peroxide organic carboxylic acid solution |
-
2019
- 2019-07-04 CN CN201910601029.8A patent/CN110283111A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070639A (en) * | 1991-09-20 | 1993-04-07 | 宇部兴产株式会社 | The preparation method of perpropionic acid |
| CN106349140A (en) * | 2016-10-26 | 2017-01-25 | 湖南聚仁化工新材料科技有限公司 | Method for preparing anhydrous peroxide organic carboxylic acid solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032565A (en) * | 2021-11-12 | 2022-02-11 | 万华化学集团股份有限公司 | Preparation method and application of anhydrous peroxycarboxylic acid |
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